TWI416108B - Quartz sensor and sensing device - Google Patents
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Abstract
Description
本發明係有關一種石英感測器及感測裝置,係可於液相中以高可靠性測定感測對象物者。The present invention relates to a quartz sensor and a sensing device capable of measuring a sensing object with high reliability in a liquid phase.
作為感測、測定微量物質之感測器係利用例如使用了石英振動元件之石英感測器。石英感測器係一種於石英板表面形成吸附層,當該吸附層表面附著感測對象物時,根據該附著之感測對象物之重量而藉由質量附加效果使石英固有振動數變化,並利用該變化之性質來測定感測對象物濃度之感測器。前述吸附層係使用如蛋白質等抗體,利用抗原抗體反應,進行樣品液(如血液)中之抗原吸附(因反應產生之捕捉)。As a sensor for sensing and measuring a trace substance, for example, a quartz sensor using a quartz vibration element is used. The quartz sensor is an adsorption layer formed on the surface of the quartz plate. When the surface of the adsorption layer is attached to the sensing object, the natural vibration number of the quartz is changed by the mass addition effect according to the weight of the attached sensing object, and A sensor that measures the concentration of the sensing object using the nature of the change. The adsorption layer uses an antibody such as a protein to carry out antigen adsorption in a sample solution (such as blood) by antigen-antibody reaction (capture by reaction).
如專利文獻1中所揭示,用於前述石英感測器的石英振動元件,有一種AT切割石英板之表面及裏面形成有電極而稱為垂直電場激勵型石英振動元件,此時,表面側電極係形成有吸附層。該種石英振動元件,就例如9MHz的石英振動元件而言,於氣相中之等效電路的串聯電阻為10Ω左右,但於液相(如純水)中前述串聯電阻會變為200~300Ω左右。就具有前述石英振動元件之石英感測器而言,前述串聯電阻係根據溶液黏性而變化,但因為於液相中之串聯電阻較小而使因溶液黏性造成之變化程度較大,因此對於振盪時的共振頻率變化帶來影響,致使測定結果的可靠性降低。為了使前述串聯電阻的變化程度不影響共振頻率或將影響降低至可忽視程度,可將石英感測器構造成石英振動元件的串聯電阻取較大之值,如3kΩ。As disclosed in Patent Document 1, a quartz vibration element used in the above quartz sensor has a surface of an AT-cut quartz plate and an electrode formed therein, which is called a vertical electric field excitation type quartz vibration element. At this time, the surface side electrode An adsorption layer is formed. In the quartz vibrating element, for example, a 9 MHz quartz vibrating element has a series resistance of about 10 Ω in an equivalent circuit in a gas phase, but in a liquid phase (such as pure water), the series resistance becomes 200 to 300 Ω. about. In the case of the quartz sensor having the quartz vibrating element described above, the series resistance varies depending on the viscosity of the solution, but since the series resistance in the liquid phase is small, the degree of change due to the viscosity of the solution is large, The influence on the resonance frequency change at the time of oscillation causes the reliability of the measurement result to decrease. In order to make the degree of change of the series resistance not affect the resonance frequency or reduce the influence to a negligible degree, the quartz sensor can be constructed such that the series resistance of the quartz vibration element takes a larger value, such as 3 kΩ.
另一方面,垂直電場激勵型之石英振動元件,與氣相中相較下,液相中之Q值(f0 /△f:f0 為共振頻率,△f於共振曲線上相當於共振電流最大值的1/√2頻帶(共振曲線的寬度))較低,舉例言之,於大氣中Q值約為60000,但於水中Q值則降低至2000左右。一般而言,若Q值低,石英振動元件之穩定性較差且電子雜訊較大,所以即使使用石英振動元件,在液相中之測定仍潛在前述課題,因此乃期待能確保更高可靠性之技術。On the other hand, the vertical electric field excitation type quartz vibration element has a Q value in the liquid phase compared with the gas phase (f 0 /Δf: f 0 is a resonance frequency, and Δf corresponds to a resonance current on the resonance curve The 1/√2 band of the maximum value (the width of the resonance curve) is low. For example, the Q value in the atmosphere is about 60,000, but the Q value in the water is reduced to about 2000. In general, if the Q value is low, the stability of the quartz vibration element is poor and the electronic noise is large. Therefore, even if a quartz vibration element is used, the measurement in the liquid phase is still a potential problem, and therefore it is expected to ensure higher reliability. Technology.
專利文獻1 特開2006─78181Patent Document 1 Special Opening 2006-78181
有鑑於前述情事,本發明之目的在於提供一種當測定樣品液中之感測對象物時,能得到高可靠性之石英感測器及感測裝置。In view of the foregoing, it is an object of the present invention to provide a quartz sensor and a sensing device which can obtain high reliability when measuring a sensing object in a sample liquid.
本發明之石英感測器,係於AT切割的石英板板面形成有用以捕捉樣品液中之感測對象物的捕捉層,且因該捕捉層上捕捉到感測對象物而使石英板之固有振動數變化,並根據該變化而感測感測對象物者,其特徵在於,於前述石英板之互相相對之端面上,設置用以使該石英板振動之電極。The quartz sensor of the present invention is formed on a surface of an AT-cut quartz plate to form a capture layer for capturing a sensing object in the sample liquid, and the quartz plate is obtained by capturing the sensing object on the capture layer. The number of natural vibrations is changed, and the object to be sensed is sensed based on the change, and an electrode for vibrating the quartz plate is provided on the mutually opposite end faces of the quartz plate.
另外,石英感測器宜採用如下構造。In addition, the quartz sensor is preferably constructed as follows.
1、於前述石英板之板面上,形成與前述電極絕緣之金屬層,且前述捕捉層形成於該金屬層。1. A metal layer insulated from the electrode is formed on a surface of the quartz plate, and the capturing layer is formed on the metal layer.
2、將設置於前述石英板端面之電極作為第1電極時,於前述石英板兩板面之各自一部分設置互相相對的第2電極,且前述第1電極及第2電極互相電連接。2. When the electrode provided on the end face of the quartz plate is used as the first electrode, a second electrode facing each other is provided on each of the two plate faces of the quartz plate, and the first electrode and the second electrode are electrically connected to each other.
3、前述第1電極及第2電極,於石英板上互相電連接。3. The first electrode and the second electrode are electrically connected to each other on a quartz plate.
本發明之感測裝置,其特徵在於具有前述石英感測器、連接至該石英感測器之振盪電路、及用以測定來自該振振盪電路之頻率信號的測定部。A sensing device according to the present invention includes the quartz sensor, an oscillation circuit connected to the quartz sensor, and a measuring unit for measuring a frequency signal from the oscillation circuit.
依據本發明,係於使用AT切割石英板之石英感測器中,於石英板板面設置捕捉層,並於板面之Z’方向上相對之端面設置電極,構成平衡電場激勵型石英振動元件,所以即使在液相中也能取得高Q值,因此頻率可靠性高,能進行樣品液中感測對象物的高可靠性測定。According to the present invention, in the quartz sensor using the AT-cut quartz plate, a trap layer is disposed on the surface of the quartz plate, and electrodes are disposed on opposite end faces in the Z' direction of the plate surface to form a balanced electric field excitation type quartz vibration element. Therefore, even if a high Q value can be obtained in the liquid phase, the frequency reliability is high, and high-reliability measurement of the sensing object in the sample liquid can be performed.
第1圖係顯示本發明實施形態之石英感測器立體圖。Fig. 1 is a perspective view showing a quartz sensor according to an embodiment of the present invention.
第2(a)、(b)圖係顯示組裝於本發明實施形態之石英感測器之石英振動元件立體圖及剖面圖。2(a) and 2(b) are a perspective view and a cross-sectional view showing a quartz resonator element incorporated in a quartz sensor according to an embodiment of the present invention.
第3圖係構成前述石英感測器一部分之印刷基板上視圖。Fig. 3 is a top view of a printed substrate constituting a part of the aforementioned quartz sensor.
第4(a)、(b)圖係顯示前述石英感測器之縱剖面圖及放大圖。4(a) and 4(b) are a longitudinal sectional view and an enlarged view showing the quartz sensor.
第5圖係顯示前述石英感測器之上視圖。Figure 5 is a top view showing the aforementioned quartz sensor.
第6圖係顯示本發明之感測裝置之立體圖。Figure 6 is a perspective view showing the sensing device of the present invention.
第7圖係一個使用前述石英感測器進行測定之測定結果例。Fig. 7 is an example of the measurement results measured using the aforementioned quartz sensor.
第8圖係顯示前述感測裝置之構成圖。Fig. 8 is a view showing the configuration of the aforementioned sensing device.
第9圖係顯示其它實施形態之石英感測器縱剖面圖。Fig. 9 is a longitudinal sectional view showing a quartz sensor of another embodiment.
第10圖係顯示其它實施形態之石英板立體圖。Fig. 10 is a perspective view showing a quartz plate of another embodiment.
第11圖係顯示其它實施形態之石英感測器立體圖。Fig. 11 is a perspective view showing a quartz sensor of another embodiment.
第12圖係顯示其它實施形態的石英板之立體圖。Fig. 12 is a perspective view showing a quartz plate of another embodiment.
第13圖係顯示其它實施形態之感測裝置一部分的構成圖。Fig. 13 is a view showing a configuration of a part of a sensing device of another embodiment.
第14(a)~(c)圖係說明一個前述感測裝置之測定結果例的說明圖。Fig. 14 (a) to (c) are explanatory views for explaining an example of measurement results of the above-described sensing device.
第15圖係顯示其它實施形態之石英板及石英感測器立體圖。Fig. 15 is a perspective view showing a quartz plate and a quartz sensor of another embodiment.
第16圖係顯示其它實施形態之石英感測器縱剖面圖。Fig. 16 is a longitudinal sectional view showing a quartz sensor of another embodiment.
第17(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 17 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
第18(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 18 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
第19(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。19(a) and (b) are views showing a quartz plate and a side view of another embodiment.
第20(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。20(a) and (b) are views showing a quartz plate and a side view of another embodiment.
第21(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。21(a) and (b) are views showing a quartz plate and a side view of another embodiment.
第22(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 22 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
第23(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。23(a) and (b) are views showing a quartz plate and a side view of another embodiment.
第24(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 24 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
第25(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 25 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
說明本發明實施形態之石英感測器。如第1圖所示,石英感測器具有石英振動元件10、印刷基板2及罩體3。如第2圖所示,前述石英振動元件10為例如AT切割的簧片狀石英板11,長邊沿石英的X軸延伸,短邊沿石英的Z’軸(將Z軸傾斜35°15' 之軸)延伸,厚度方向為石英的Y’軸(Y軸傾斜35°15' 之軸)。於該石英振動元件10之石英板11的其中一板面(第2(a)圖中上面:XZ’面)上,金屬層11a(參照第2(b)圖)形成圓形,且該金屬層表面形成有捕捉層(吸附層)12,該捕捉層12係藉由抗原抗體反應來捕捉例如作為感測對象物之抗原者。前述金屬層11(a)係於例如作為密著層之鉻(Cr)的上面層疊金而構成。前述石英板11 Z’方向之互相相對之端面形成有用以使該石英板11振盪之電極13,另外這些電極13之下端部係卷繞至石英板11的另一面側(第2(a)圖的下側),而連接至後述印刷基板之導電路。前述金屬層11a及電極13係依據例如光刻法同時形成。另外,在石英板11上捕捉層12的外緣區域,即與後述罩體的圓筒體下端部相對向之部位,環狀地形成有撥水層14。該撥水層14係防止樣品液由撥水層14與圓筒體下端部間之間隙流出。A quartz sensor according to an embodiment of the present invention will be described. As shown in FIG. 1, the quartz sensor has a quartz vibration element 10, a printed circuit board 2, and a cover 3. As shown in Fig. 2, the quartz resonator element 10 is, for example, an AT-cut reed-shaped quartz plate 11 having a long side extending along the X-axis of the quartz and a short side along the Z'-axis of the quartz (the axis of the Z-axis is inclined by 35° 15 ' ) Extension, the thickness direction is the Y' axis of quartz (the axis of the Y axis is inclined by 35° 15 ' ). On one of the plate faces (the upper surface of the second (a): XZ' plane) of the quartz plate 11 of the quartz resonator element 10, the metal layer 11a (see FIG. 2(b)) is formed into a circular shape, and the metal A trap layer (adsorption layer) 12 is formed on the surface of the layer, and the trap layer 12 captures, for example, an antigen as a sensing object by an antigen-antibody reaction. The metal layer 11 (a) is formed by, for example, laminating gold on the upper surface of chromium (Cr) as an adhesion layer. The opposite end faces of the quartz plate 11 in the Z' direction form an electrode 13 for oscillating the quartz plate 11, and the lower end portions of the electrodes 13 are wound around the other side of the quartz plate 11 (Fig. 2(a) The lower side) is connected to a conductive circuit of a printed circuit board to be described later. The metal layer 11a and the electrode 13 are simultaneously formed by, for example, photolithography. Moreover, the water-repellent layer 14 is formed in an annular shape in the outer edge region of the trap layer 12 on the quartz plate 11, that is, a portion facing the lower end portion of the cylindrical body of the cover body to be described later. The water-repellent layer 14 prevents the sample liquid from flowing out from the gap between the water-repellent layer 14 and the lower end portion of the cylindrical body.
如第3圖所示,前述印刷基板2由其表面之一端側向另一端平行地設置有導電路21a、21b。另外導電路21a、21b的一端側形成有用以與後述間隔件側之電極連接的電極22a、22b,導電路21a、21b另一端側具有用以與後述振盪電路的連接端子部連接之連接端子作用。As shown in Fig. 3, the printed circuit board 2 is provided with conductive circuits 21a and 21b in parallel from one end side to the other end. Further, on one end side of the conductive circuits 21a and 21b, electrodes 22a and 22b for connecting to electrodes on the spacer side to be described later are formed, and the other end sides of the conductive circuits 21a and 21b have connection terminals for connection to connection terminal portions of an oscillation circuit to be described later. .
如第1及4(a)圖所示,設置有方形之箱狀罩體3,以覆蓋前述印刷基板2之一端側區域。在此,若將朝印刷基板之長方向延伸的兩邊緣分別稱為左邊緣,右邊緣,則罩體3的3邊係各自沿著印刷基板2的一端緣、左邊緣、右邊緣形成。前述罩體3和印刷基板2之間具有簧片狀間隔件51a、51b,該等間隔件51a、51b係由各自沿著左右兩邊緣之例如樹脂或橡膠等所構成。前述石英振動元件10中,不設置電極且朝X方向互相相對向之邊緣部係設置成橫跨間隔件11,而與印刷基板2的左邊緣(右邊緣)平行,該邊緣部與該間隔件51a、51b的接觸位置比後述樣品液的液體容納空間還靠外側。As shown in Figs. 1 and 4(a), a square box-shaped cover 3 is provided to cover one end side region of the printed circuit board 2. Here, if both edges extending in the longitudinal direction of the printed substrate are referred to as a left edge and a right edge, respectively, the three sides of the cover 3 are formed along the one end edge, the left edge, and the right edge of the printed circuit board 2, respectively. The reed-like spacers 51a and 51b are provided between the cover 3 and the printed circuit board 2, and the spacers 51a and 51b are made of, for example, resin or rubber, respectively, along the left and right edges. In the quartz vibrating element 10, the electrodes are not provided with the electrodes and are disposed opposite to each other in the X direction so as to straddle the spacer 11 in parallel with the left edge (right edge) of the printed substrate 2, the edge portion and the spacer The contact positions of 51a and 51b are further outside than the liquid storage space of the sample liquid to be described later.
如第4(a)圖所示,於間隔件51a、51b的上下兩面形成電極(無圖示),為使這些電極互相連接,該間隔件51a、51b的厚度方向設置有導電路52a、52b。該間隔件51a、51b之上面側電極與石英振動元件10之下面側電極13(參照第2(b)圖)接觸,間隔件51a、51b之下面側電極分別與印刷基板2的導電路21a、21b的端部(電極)22a、22b接觸。因此,若施加電壓於印刷基板2的導電路21a、21b,石英振動元件10的電極13就會被施加電壓。As shown in Fig. 4(a), electrodes (not shown) are formed on the upper and lower surfaces of the spacers 51a and 51b. In order to connect the electrodes to each other, the spacers 51a and 51b are provided with the conductive circuits 52a and 52b in the thickness direction. . The upper surface electrodes of the spacers 51a and 51b are in contact with the lower surface electrode 13 of the quartz resonator element 10 (see FIG. 2(b)), and the lower surface electrodes of the spacers 51a and 51b are respectively connected to the conductive circuit 21a of the printed circuit board 2, The ends (electrodes) 22a, 22b of 21b are in contact. Therefore, when a voltage is applied to the conductive circuits 21a and 21b of the printed circuit board 2, a voltage is applied to the electrodes 13 of the quartz resonator element 10.
如第4及5圖所示,罩體3的中央部分開口,圓筒體31從開口邊向下方延伸。該圓筒體31的下邊緣係較石英振動元件10的表面略微靠上方。前述圓筒體31和石英振動元件10表面所包圍的區域構成容納樣品液的液體容納空間32。另外,圓筒體31由撥水性材料構成,藉由前述石英板11表面形成的前述撥水層14回彈樣品液,並利用其表面張力使樣品液從容納空間32不會透過前述圓筒體31的下邊緣和石英振動元件10表面間之間隙而向外漏出(參照第4(b)圖)。As shown in Figs. 4 and 5, the central portion of the cover 3 is opened, and the cylindrical body 31 extends downward from the opening side. The lower edge of the cylindrical body 31 is slightly above the surface of the quartz vibration element 10. The area surrounded by the cylindrical body 31 and the surface of the quartz resonator element 10 constitutes a liquid accommodating space 32 for accommodating the sample liquid. Further, the cylindrical body 31 is made of a water-repellent material, and the water-repellent layer 14 formed on the surface of the quartz plate 11 rebounds the sample liquid, and the surface tension thereof prevents the sample liquid from passing through the cylindrical body from the accommodating space 32. A gap between the lower edge of 31 and the surface of the quartz resonator element 10 leaks outward (refer to Fig. 4(b)).
接著,說明感測裝置6。如第6圖所示,感測裝置6具有前述石英振動元件1、包含一將該石英振動元件上安裝成可裝卸自由的振盪電路之振盪電路單元4、及包含感測器主體61與例如個人電腦62的測定部。前述石英感測器1係印刷基板2的端子部(導電路)21a、21b連接至振盪電路單元4的端子部49,該振盪電路單元4透過例如同軸電纜與感測器主體61電連接。前述振盪電路單元4內的振盪電路係構造成柯比玆型振盪電路單元,具有使石英感測器1之石英振動元件10振盪的作用。第8圖中Tr係作為振盪放大元素的電晶體,40、41係構成分割電容成份(divided capacitive components)的電容,Vcc為恒壓電源。關於其它部份,42~44為電容,45~48為電阻。前述振盪電路單元4的後段透過緩衝放大器63連接有感測器主體61。前述感測器主體61具有測定與振盪電路單元4的振盪輸出頻率相關之信號之機能。頻率之測定方法可使用頻率計數器,也可正交檢測頻率信號,計算利用一該頻率信號的頻率和使用檢測的頻率信號的頻率之差的頻率而旋轉之旋轉向量,並將該旋轉向量的相位變化評價為旋轉向量的速度,以求取該速度。Next, the sensing device 6 will be described. As shown in Fig. 6, the sensing device 6 includes the quartz resonator element 1, an oscillating circuit unit 4 including a detachable oscillating circuit mounted on the quartz vibration element, and a sensor body 61 and, for example, an individual. The measurement unit of the computer 62. The quartz sensor 1 is a terminal portion (guide circuit) 21a, 21b of the printed circuit board 2, which is connected to the terminal portion 49 of the oscillating circuit unit 4, and the oscillating circuit unit 4 is electrically connected to the sensor main body 61 via, for example, a coaxial cable. The oscillation circuit in the oscillation circuit unit 4 is configured as a Kirz-type oscillation circuit unit, and has a function of oscillating the quartz vibration element 10 of the quartz sensor 1. In Fig. 8, Tr is a transistor which is an oscillation amplifying element, 40 and 41 are capacitors of divided capacitive components, and Vcc is a constant voltage source. For other parts, 42 to 44 are capacitors, and 45 to 48 are resistors. The sensor main body 61 is connected to the rear stage of the oscillation circuit unit 4 through the buffer amplifier 63. The aforementioned sensor body 61 has a function of measuring a signal related to the oscillation output frequency of the oscillation circuit unit 4. The frequency measurement method may use a frequency counter or a quadrature detection frequency signal, and calculate a rotation vector rotated by a frequency of the frequency signal and a frequency difference between the frequencies of the detected frequency signals, and the phase of the rotation vector The change is evaluated as the speed of the rotation vector to find the speed.
下一步說明使用具有前述構成之石英感測器1及感測裝置6來測定感測對象物(例如血液或血清中某種抗原之濃度)之步驟。首先,將石英感測器1插入感測裝置6的振盪電路單元4的插口,藉由該插入使印刷基板2的端子部(導電路)21a、21b和振盪電路單元4的端子部49電連接。接著,利用振盪電路單元4使石英振動元件10振盪,並將經振盪之頻率信號輸入感測器主體61。然後,測定者從石英感測器1的罩體3開口部注入例如食鹽水來作為稀釋液,於是液體容納空間32充滿食鹽水,石英振動元件10的環境由氣相變成液相,測定此時之頻率。接下來,當將血清保持原狀或以例如食鹽水稀釋後的樣品液從前述開口部注入石英感測器1的液體收納空間32,依據該樣品液中含有的抗原與吸附層的抗體發生抗原抗體反應而捕捉。隨著該抗原抗體反應進行,頻率值會因質量負載效果而降低。然後,如第7圖所示,依據例如連接至感測器主體61的個人電腦62,求取例如74Hz的頻率變化程度,並根據例如事先做好的標準曲線測出感測對象物之濃度。Next, the step of measuring the object to be sensed (for example, the concentration of an antigen in blood or serum) using the quartz sensor 1 and the sensing device 6 having the above-described configuration will be described. First, the quartz sensor 1 is inserted into the socket of the oscillation circuit unit 4 of the sensing device 6, and the terminal portions (guide circuits) 21a, 21b of the printed substrate 2 and the terminal portions 49 of the oscillation circuit unit 4 are electrically connected by the insertion. . Next, the quartz vibration element 10 is oscillated by the oscillation circuit unit 4, and the oscillated frequency signal is input to the sensor main body 61. Then, the measurer injects, for example, saline into the opening of the cover 3 of the quartz sensor 1 as a diluent, so that the liquid storage space 32 is filled with the saline solution, and the environment of the quartz resonator element 10 changes from the gas phase to the liquid phase, and the measurement is performed at this time. The frequency. Next, the sample liquid which has been kept in the original state or diluted with, for example, saline, is injected into the liquid storage space 32 of the quartz sensor 1 from the opening, and an antigen-antibody is generated depending on the antigen contained in the sample liquid and the antibody of the adsorption layer. Capture by reaction. As the antigen-antibody reaction proceeds, the frequency value decreases due to the mass loading effect. Then, as shown in Fig. 7, the degree of frequency change of, for example, 74 Hz is obtained in accordance with, for example, the personal computer 62 connected to the sensor main body 61, and the concentration of the sensing object is measured based on, for example, a standard curve prepared in advance.
前述罩體3的圓筒體31下端部也可如第9圖所示向外側彎曲形成凸緣狀。The lower end portion of the cylindrical body 31 of the cover body 3 may be bent outward to form a flange shape as shown in Fig. 9.
另外,前述金屬層11a之形狀係形成為長方形,如第10圖所示,也可於其上形成捕捉層12。此時,如第11圖所示,可設置成罩體3之開口部開口成長方形,且方形筒體31由開口邊緣伸出,以配合捕捉層12的形狀。Further, the shape of the metal layer 11a is formed in a rectangular shape, and as shown in Fig. 10, the trap layer 12 may be formed thereon. At this time, as shown in Fig. 11, the opening portion of the cover 3 may be opened to have a rectangular shape, and the square cylindrical body 31 is extended by the opening edge to match the shape of the trap layer 12.
依據前述實施形態,石英感測器1使用AT切割的石英板11,於該石英板11板面設置捕捉層12,並於板面Z’方向互相相對之端面設置電極13而構成平衡電場激勵型之石英振動元件10,所以即使於液相中也能取得高Q值,因此頻率穩定性高,對於感測對象物能進行高可靠性之測定。According to the above embodiment, the quartz sensor 11 is an AT-cut quartz plate 11, a trap layer 12 is provided on the surface of the quartz plate 11, and electrodes 13 are disposed on opposite end faces of the plate surface Z' to form a balanced electric field excitation type. Since the quartz resonator element 10 can obtain a high Q value even in a liquid phase, the frequency stability is high, and high-reliability measurement can be performed on the object to be sensed.
接著,說明本發明其它實施形態之石英感測器。如第12圖所示,石英感測器1採用的石英板11之端面中央部形成有構成彈性邊界層之溝部100,依據此溝部100,石英板11被分割成2部分:第1振動區域(左側區域)101和第2振動區域(右側區域)102。在前述第1振動區域101之石英板11板面上,形成有由不會透過金屬層與感測對象物反應的抗體構成的區塊層103,且各端面形成有電極13a。在前述第2振動區域102之石英板11板面上,層疊金屬層11a形成捕捉層12,且各端面形成有電極13b。另外電極13a、13b捲繞至石英板11的另一面側(下面側)。Next, a quartz sensor according to another embodiment of the present invention will be described. As shown in Fig. 12, a central portion of the end surface of the quartz plate 11 used in the quartz sensor 1 is formed with a groove portion 100 constituting an elastic boundary layer. According to the groove portion 100, the quartz plate 11 is divided into two parts: a first vibration region ( The left area) 101 and the second vibration area (right area) 102. On the plate surface of the quartz plate 11 of the first vibrating region 101, a block layer 103 composed of an antibody that does not transmit a metal layer and react with a sensing object is formed, and an electrode 13a is formed on each end surface. On the plate surface of the quartz plate 11 of the second vibrating region 102, the metal layer 11a is laminated to form the trap layer 12, and the electrode 13b is formed on each end surface. Further, the electrodes 13a and 13b are wound around the other surface side (lower side) of the quartz plate 11.
然後,石英感測器1插入振盪電路單元4,藉此將第1振動區域101側的其中一電極13a連接至振盪電路111同時另一電極13a接地,且將第2振動區域102側的其中一電極13b連接至振盪電路112同時另一電極13b接地。Then, the quartz sensor 1 is inserted into the oscillation circuit unit 4, whereby one of the electrodes 13a on the side of the first vibration region 101 is connected to the oscillation circuit 111 while the other electrode 13a is grounded, and one of the sides of the second vibration region 102 is placed. The electrode 13b is connected to the oscillation circuit 112 while the other electrode 13b is grounded.
前述石英感測器1中,第1振動區域不隨吸附感測對象物產生的變化而變化,可測定無關於樣品溶液的濃度而僅因溫度而變化之振盪頻率「F0」(第14圖的(a)),另外於第2振動區域能測定基於吸附感測對象物之樣品液濃度、基於溫度之振盪頻率「F1」(第14圖的(b))。而且,即使當石英板11周圍發生溫度變化時,前述振盪頻率「F0」及「F1」也會在同一條件下受到溫度變化的影響。故,藉由計算振盪頻率的差分「F1-F0」,可得到除去溫度變化導致之頻率變化的高可靠性測定結果(第14圖的(c))。In the quartz sensor 1, the first vibration region does not change with the change in the object to be sensed, and the oscillation frequency "F0" which varies depending only on the temperature regardless of the concentration of the sample solution can be measured (Fig. 14) (a)) In addition, in the second vibration region, the sample liquid concentration based on the adsorption sensing target and the oscillation frequency "F1" based on the temperature can be measured (Fig. 14 (b)). Further, even when a temperature change occurs around the quartz plate 11, the oscillation frequencies "F0" and "F1" are affected by the temperature change under the same conditions. Therefore, by calculating the difference "F1-F0" of the oscillation frequency, it is possible to obtain a highly reliable measurement result in which the frequency change due to the temperature change is removed ((c) of Fig. 14).
另外,本發明其它實施形態之石英感測器,如第15圖所示,於印刷基板2的一端側區域設置上部開口的箱體201。該箱體201內之兩端部分別設置有載置構件202,該載置構件202係用以載置向印刷基板2的寬度方向延伸的石英板11者。石英振動元件10係載置於該載置構件202,並使用例如導電性黏合劑加以固定,使形成有電極13之端面與載置構件202正交。前述石英振動元件10的捕捉層12與前述實施形態相同地,形成於與石英板11端面的電極13分離(絕緣)之金屬層表面。而且,如第16圖所示,由於載置構件202表面形成有導電路203a、203b,因此可藉由石英板11載置於載置構件202,將捲繞至石英板11下面側的電極13和導電路203a、203b的一端連接。導電路203a、203b另一端從箱體201底部伸出,各自連接至印刷基板2的導電路21a、21b。本實施形態中,石英板11的端面(形成有電極13之面)和箱體201的側面有縫隙,液體容納空間204不僅包括由形成有石英板11的捕捉層12之面和箱體201包圍的空間,也包括由石英板11下面(裏面)和箱體201包圍的空間。Further, in the quartz sensor according to another embodiment of the present invention, as shown in Fig. 15, a case 201 having an upper opening is provided in one end side region of the printed circuit board 2. Each of the both ends of the casing 201 is provided with a mounting member 202 for placing a quartz plate 11 extending in the width direction of the printed circuit board 2. The quartz resonator element 10 is placed on the mounting member 202 and fixed by, for example, a conductive adhesive, and the end surface on which the electrode 13 is formed is orthogonal to the mounting member 202. The trap layer 12 of the quartz resonator element 10 is formed on the surface of the metal layer separated (insulated) from the electrode 13 on the end surface of the quartz plate 11 in the same manner as in the above embodiment. Further, as shown in Fig. 16, since the conductive members 203a and 203b are formed on the surface of the mounting member 202, the quartz plate 11 can be placed on the mounting member 202, and the electrode 13 wound to the lower surface side of the quartz plate 11 can be wound. It is connected to one end of the conductive circuits 203a and 203b. The other ends of the lead circuits 203a and 203b protrude from the bottom of the case 201, and are respectively connected to the lead circuits 21a and 21b of the printed circuit board 2. In the present embodiment, the end surface of the quartz plate 11 (the surface on which the electrode 13 is formed) and the side surface of the casing 201 have slits, and the liquid accommodation space 204 includes not only the surface of the trap layer 12 on which the quartz plate 11 is formed but also the casing 201. The space also includes a space surrounded by the underside (inside) of the quartz plate 11 and the casing 201.
以下記載石英振動元件的其它例子。如第17~20圖所示,石英振動元件10的捕捉層12皆不隔著金屬層形成於石英板11上,但亦可如先前之實施形態,構造成和石英板11端面的電極分離而於石英板11板面形成金屬層,並層疊於其上。另外,第17(a)、(b)圖例子中,設置已於石英板11端面的寬度方向整個形成電極311的區域、以及從該電極311伸出而已於端面寬度方向中央部形成電極311的區域,並主要利用前者的電極使石英板11振動,而後者的電極則用於和外部的電極連接。Other examples of the quartz resonator element are described below. As shown in FIGS. 17 to 20, the trap layer 12 of the quartz resonator element 10 is formed not on the quartz plate 11 via the metal layer, but may be configured to be separated from the electrode on the end surface of the quartz plate 11 as in the previous embodiment. A metal layer is formed on the surface of the quartz plate 11 and laminated thereon. In the example of the seventeenth (a) and (b), the region in which the electrode 311 is formed in the entire width direction of the end surface of the quartz plate 11 and the electrode 311 are formed in the central portion of the end face width direction. The region, and mainly uses the former electrode to vibrate the quartz plate 11, and the latter electrode is used to connect with the external electrode.
第18(a)、(b)圖之例中,於石英板11端面之一端側及另一端側間隔地設置電極321,各個電極321捲繞至石英板11下面。換言之,該例中於石英板11的Z’方向互相相對的電極組係沿石英板11長度方向形成2組。此時,各組電極中形成於同一端面的2個電極係例如連接至共通之導電路。第19(a)、(b)圖所示之例中,係對於第18圖所示形成於同一端面的2個電極,適用了第17圖的構造。另外,石英振動元件也可於石英板11的兩面設置捕捉層12,而作為此例適用於第19圖構成的例子則顯示第20圖。In the example of Figs. 18(a) and (b), the electrode 321 is provided at one end side and the other end side of the end surface of the quartz plate 11, and the respective electrodes 321 are wound around the lower surface of the quartz plate 11. In other words, in this example, the electrode groups opposed to each other in the Z' direction of the quartz plate 11 are formed in two groups along the longitudinal direction of the quartz plate 11. At this time, the two electrodes formed on the same end surface of each group of electrodes are connected to, for example, a common conduction circuit. In the examples shown in Figs. 19(a) and (b), the structure of Fig. 17 is applied to the two electrodes formed on the same end surface shown in Fig. 18. Further, the quartz resonator element may be provided with the trap layer 12 on both surfaces of the quartz plate 11, and as an example of the configuration of Fig. 19, Fig. 20 is shown.
另外,第21~24圖所示之例,係不僅於石英板11的端面也沿板面(上面)之左邊緣及右邊緣設置電極,甚至於石英板11下面也沿著左邊緣及右邊緣設置電極。這些例子都是將捕捉層12設置於石英板11的整個板面,且呈設置於板面上形成的電極341a、341b(351a、352a)上之狀態,因此可從導電路得到,平行電場激勵產生之頻率信號與垂直電場激勵產生之頻率信號重疊的頻率信號。因此,能更高感度地檢測出頻率信號。在此,第21及22圖之例子,係石英板11上面電極的大小和下面電極的大小彼此不同,亦即產生垂直電場激勵的電極組非對稱。相對於此,第23及24圖之例子,係石英板11上面電極的大小和下面電極的大小相同,亦即產生垂直電場激勵的電極組對稱。另外,第21~23圖係於石英板11之一面側設置捕捉層12之例,第24圖係於石英板兩面設置捕捉層12之例。Further, in the examples shown in Figs. 21 to 24, electrodes are provided not only on the end faces of the quartz plate 11, but also on the left and right edges of the plate surface (upper surface), even under the quartz plate 11 along the left and right edges. Set the electrodes. In these examples, the trap layer 12 is disposed on the entire surface of the quartz plate 11 and is disposed on the electrodes 341a, 341b (351a, 352a) formed on the surface of the board, and thus can be obtained from the conductive circuit, and the parallel electric field is excited. A frequency signal in which the generated frequency signal overlaps with the frequency signal generated by the vertical electric field excitation. Therefore, the frequency signal can be detected with higher sensitivity. Here, in the examples of Figs. 21 and 22, the size of the upper electrode of the quartz plate 11 and the size of the lower electrode are different from each other, that is, the electrode group which generates the vertical electric field excitation is asymmetric. On the other hand, in the examples of Figs. 23 and 24, the size of the upper electrode of the quartz plate 11 is the same as the size of the lower electrode, that is, the electrode group which generates the vertical electric field excitation is symmetrical. Further, the 21st to 23rd drawings are examples in which the capturing layer 12 is provided on one surface side of the quartz plate 11, and the 24th drawing is an example in which the capturing layer 12 is provided on both surfaces of the quartz plate.
不僅產生平行電場激勵而且產生垂直電場激勵的電極構造可適用於第2或12圖所示之實施形態,但是垂直電場激勵程度大Q值就低,所以為能確保高Q值最好設定垂直電場激勵的程度。如第25圖所示,在石英板11兩面,與形成於石英板11端面連續的電極361係僅形成於左右兩邊緣,並於這些電極361之石英板11上面側的電極上形成捕捉層12,且於石英板11上面側形成與端面側的電極361分離之金屬層11a,以於該金屬層11a上形成捕捉層12。An electrode structure that generates not only parallel electric field excitation but also vertical electric field excitation can be applied to the embodiment shown in FIG. 2 or FIG. 12, but the vertical electric field excitation degree is large and the Q value is low, so it is preferable to set a vertical electric field in order to ensure a high Q value. The degree of motivation. As shown in Fig. 25, on both sides of the quartz plate 11, the electrode 361 which is continuous with the end surface of the quartz plate 11 is formed only on the left and right edges, and the trap layer 12 is formed on the electrode on the upper surface side of the quartz plate 11 of these electrodes 361. A metal layer 11a separated from the electrode 361 on the end surface side is formed on the upper surface side of the quartz plate 11 to form the trap layer 12 on the metal layer 11a.
接著,進行本發明實施形態之石英感測器的測定實驗。Next, a measurement experiment of the quartz sensor of the embodiment of the present invention was carried out.
實驗使用之石英感測器是使用實施形態所說明之第18、20及23圖的三種石英振動元件,並於測定環境為大氣中和磷酸緩衝生理食鹽水(PBS: Phosphate buffered saline)中進行石英感測器之等效電路常數(串聯電阻R、電感L、電容C及Q值)的測定。The quartz sensor used in the experiment is three kinds of quartz vibrating elements according to the 18th, 20th, and 23th embodiments described in the embodiment, and is subjected to quartz in the atmosphere and in phosphate buffered saline (PBS: Phosphate buffered saline). Determination of the equivalent circuit constant of the sensor (series resistance R, inductance L, capacitance C and Q value).
測定結果顯示於下表。表1顯示將第18圖的石英振動元件用於石英感測器、表2顯示將第20圖的石英振動元件用於石英感測器、表3顯示將第23圖的石英振動元件用於石英感測器時進行測定之結果。還有,測定環境由氣相變為液相時的頻率差分,在第18圖的石英振動元件為131Hz,在第20圖的石英振動元件為132 Hz,在第23圖的石英振動元件為64 Hz。The results of the measurements are shown in the table below. Table 1 shows that the quartz vibration element of Fig. 18 is used for a quartz sensor, Table 2 shows that the quartz vibration element of Fig. 20 is used for a quartz sensor, and Table 3 shows that the quartz vibration element of Fig. 23 is used for quartz. The result of the measurement at the time of the sensor. Further, the frequency difference in the measurement environment from the gas phase to the liquid phase is 131 Hz in the quartz resonator element of Fig. 18, 132 Hz in the quartz resonator element in Fig. 20, and 64 in the quartz resonator element in Fig. 23 Hz.
第18、20及23圖無論於哪個石英振動元件,串聯電阻(R)均變化很小,可知石英振動元件的串聯電阻大到可忽視該變化。還有,Q值即使比較於大氣中與於PBS中亦大致相同,所以可知即使於液相中頻率穩定性也高,能高精度檢測出感測對象物。Figures 18, 20, and 23 show that the series resistance (R) varies little regardless of the quartz vibration element. It is known that the series resistance of the quartz vibration element is so large that the change can be ignored. Further, even if the Q value is substantially the same as that in the PBS, it is found that the frequency stability is high even in the liquid phase, and the object to be sensed can be detected with high precision.
1...石英感測器1. . . Quartz sensor
2...印刷基板2. . . Printed substrate
3...罩體3. . . Cover
4...振盪電路裝置4. . . Oscillating circuit device
6...感測裝置6. . . Sensing device
10...石英振動元件10. . . Quartz vibrating element
11...石英板11. . . Quartz plate
11a...金屬層11a. . . Metal layer
12...捕捉層12. . . Capture layer
13...電極13. . . electrode
13a、b...電極13a, b. . . electrode
14...撥水層14. . . Water layer
21a、b...導電路21a, b. . . Guide circuit
22a、b...電極22a, b. . . electrode
31...圓筒體31. . . Cylinder
32...液體容納空間32. . . Liquid holding space
40~44...電容40~44. . . capacitance
45~48...電阻45~48. . . resistance
49...端子部49. . . Terminal part
51a、b...間隔件51a, b. . . Spacer
52a、b...導電路52a, b. . . Guide circuit
61...感測器主體61. . . Sensor body
62...個人電腦62. . . personal computer
63...緩衝放大器63. . . Buffer amplifier
100...溝部100. . . Ditch
101...第1振動區域101. . . First vibration zone
102...第2振動區域102. . . Second vibration zone
103...區塊層103. . . Block layer
111、112...振盪電路111, 112. . . Oscillation circuit
201...箱體201. . . Box
202...載置構件202. . . Mounting member
203a、b...導電路203a, b. . . Guide circuit
204...液體容納空間204. . . Liquid holding space
311...電極311. . . electrode
321...電極321. . . electrode
341a、b...電極341a, b. . . electrode
351a、b...電極351a, b. . . electrode
361...電極361. . . electrode
第1圖係顯示本發明實施形態之石英感測器立體圖。Fig. 1 is a perspective view showing a quartz sensor according to an embodiment of the present invention.
第2(a)、(b)圖係顯示組裝於本發明實施形態之石英感測器之石英振動元件立體圖及剖面圖。2(a) and 2(b) are a perspective view and a cross-sectional view showing a quartz resonator element incorporated in a quartz sensor according to an embodiment of the present invention.
第3圖係構成前述石英感測器一部分之印刷基板上視圖。Fig. 3 is a top view of a printed substrate constituting a part of the aforementioned quartz sensor.
第4(a)、(b)圖係顯示前述石英感測器之縱剖面圖及放大圖。4(a) and 4(b) are a longitudinal sectional view and an enlarged view showing the quartz sensor.
第5圖係顯示前述石英感測器之上視圖。Figure 5 is a top view showing the aforementioned quartz sensor.
第6圖係顯示本發明之感測裝置之立體圖。Figure 6 is a perspective view showing the sensing device of the present invention.
第7圖係一個使用前述石英感測器進行測定之測定結果例。Fig. 7 is an example of the measurement results measured using the aforementioned quartz sensor.
第8圖係顯示前述感測裝置之構成圖。Fig. 8 is a view showing the configuration of the aforementioned sensing device.
第9圖係顯示其它實施形態之石英感測器縱剖面圖。Fig. 9 is a longitudinal sectional view showing a quartz sensor of another embodiment.
第10圖係顯示其它實施形態之石英板立體圖。Fig. 10 is a perspective view showing a quartz plate of another embodiment.
第11圖係顯示其它實施形態之石英感測器立體圖。Fig. 11 is a perspective view showing a quartz sensor of another embodiment.
第12圖係顯示其它實施形態的石英板之立體圖。Fig. 12 is a perspective view showing a quartz plate of another embodiment.
第13圖係顯示其它實施形態之感測裝置一部分的構成圖。Fig. 13 is a view showing a configuration of a part of a sensing device of another embodiment.
第14(a)~(c)圖係說明一個前述感測裝置之測定結果例的說明圖。Fig. 14 (a) to (c) are explanatory views for explaining an example of measurement results of the above-described sensing device.
第15圖係顯示其它實施形態之石英板及石英感測器立體圖。Fig. 15 is a perspective view showing a quartz plate and a quartz sensor of another embodiment.
第16圖係顯示其它實施形態之石英感測器縱剖面圖。Fig. 16 is a longitudinal sectional view showing a quartz sensor of another embodiment.
第17(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 17 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
第18(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 18 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
第19(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。19(a) and (b) are views showing a quartz plate and a side view of another embodiment.
第20(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。20(a) and (b) are views showing a quartz plate and a side view of another embodiment.
第21(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。21(a) and (b) are views showing a quartz plate and a side view of another embodiment.
第22(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 22 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
第23(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。23(a) and (b) are views showing a quartz plate and a side view of another embodiment.
第24(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 24 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
第25(a)、(b)圖係顯示其它實施形態之石英板立體圖及側面圖。Fig. 25 (a) and (b) are views showing a quartz plate and a side view of another embodiment.
10...石英振動元件10. . . Quartz vibrating element
11...石英板11. . . Quartz plate
11a...金屬層11a. . . Metal layer
12...捕捉層12. . . Capture layer
13...電極13. . . electrode
14...撥水層14. . . Water layer
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| JP2006029873A (en) * | 2004-07-13 | 2006-02-02 | Nippon Dempa Kogyo Co Ltd | Quartz sensor and sensing device |
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| JP2793728B2 (en) * | 1991-09-26 | 1998-09-03 | 富士通株式会社 | Serial / parallel conversion circuit |
| SE0004547D0 (en) * | 2000-12-07 | 2000-12-07 | Amersham Pharmacia Biotech Kk | Chip quartz oscillator and sensor |
| JP2006033195A (en) | 2004-07-13 | 2006-02-02 | Nippon Dempa Kogyo Co Ltd | Crystal oscillator and sensing device |
| JP4387896B2 (en) * | 2004-08-31 | 2009-12-24 | 光男 中澤 | QCM sensor and measurement method using QCM sensor |
| EP1830169B1 (en) * | 2004-12-15 | 2014-02-12 | Nihon Dempa Kogyo Co., Ltd. | Quartz sensor and sensing device |
| JP2007192650A (en) * | 2006-01-19 | 2007-08-02 | Citizen Holdings Co Ltd | Qcm sensor and qcm sensor device |
| US7667369B2 (en) * | 2006-11-01 | 2010-02-23 | Delaware Capital Formation, Inc. | High sensitivity microsensors based on flexure induced frequency effects |
| JP2008256583A (en) * | 2007-04-06 | 2008-10-23 | Epson Toyocom Corp | Quartz vibration element and acceleration detection device |
| JP5066551B2 (en) * | 2008-05-20 | 2012-11-07 | 日本電波工業株式会社 | Piezoelectric sensor and sensing device |
| JP4809410B2 (en) * | 2008-09-29 | 2011-11-09 | 日本電波工業株式会社 | Piezoelectric device and manufacturing method thereof |
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